JPH09104681A - Production of delta-lactone - Google Patents
Production of delta-lactoneInfo
- Publication number
- JPH09104681A JPH09104681A JP7260187A JP26018795A JPH09104681A JP H09104681 A JPH09104681 A JP H09104681A JP 7260187 A JP7260187 A JP 7260187A JP 26018795 A JP26018795 A JP 26018795A JP H09104681 A JPH09104681 A JP H09104681A
- Authority
- JP
- Japan
- Prior art keywords
- added
- formula
- hydrogen peroxide
- reaction system
- ketone compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、香料成分、あるい
は工業化学品の中間体として有用である、δ−ラクトン
化合物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a δ-lactone compound which is useful as a perfume ingredient or an intermediate for industrial chemicals.
【０００２】[0002]
【従来の技術】環状ケトン化合物を過酢酸等の酸化剤に
よって酸化し、ラクトン化合物を製造する反応は、バイ
ヤービリガー反応として古くから知られており、現在で
もラクトン化合物を得るプロセスの主流となっている。
バイヤービリガー反応において使用される酸化剤として
は、過酢酸が一般的である。この過酢酸の製造方法とし
ては、種々の方法が知られているが、過酸化水素と酢酸
を強酸触媒の存在下に反応させる方法が一般的である。2. Description of the Related Art The reaction of producing a lactone compound by oxidizing a cyclic ketone compound with an oxidizing agent such as peracetic acid has long been known as the Bayer-Villiger reaction, and is still the mainstream of the process for obtaining a lactone compound. There is.
Peracetic acid is a common oxidant used in the Bayer-Villiger reaction. Although various methods are known as methods for producing peracetic acid, a method in which hydrogen peroxide and acetic acid are reacted in the presence of a strong acid catalyst is general.
【０００３】酢酸と過酸化水素とを反応させて得られる
過酢酸を、δ−ラクトン化合物製造反応に利用するに
は、下記の方法が知られている。 （１）予め、過酢酸溶液を製造しておき、その過酢酸溶
液と環状ケトン化合物とを反応させる方法（以下、Ｐｒ
ｅｆｏｒｍｅｄ法と記す。） （２）反応系内で、酢酸と過酸化水素を接触させ、その
反応系内で過酢酸を発生させながらこれを環状ケトン化
合物と反応させる方法（以下、ｉｎ−ｓｉｔｕ法と記
す。）The following method is known to utilize peracetic acid obtained by reacting acetic acid and hydrogen peroxide in the reaction for producing a δ-lactone compound. (1) A method of producing a peracetic acid solution in advance and reacting the peracetic acid solution with a cyclic ketone compound (hereinafter, referred to as Pr
It is referred to as the eformed method. (2) A method in which acetic acid and hydrogen peroxide are brought into contact with each other in the reaction system and reacted with a cyclic ketone compound while generating peracetic acid in the reaction system (hereinafter, referred to as in-situ method).
【０００４】バイヤービリガー反応において、一般的に
は、Ｐｒｅｆｏｒｍｅｄ法の方が目的化合物の収率が高
いため、この方法が多く採用されている。しかし、この
方法は、予め過酢酸溶液を製造しておく必要があり、そ
のための製造設備、および反応工程等がδ−ラクトン製
造設備および反応工程等とは別に必要となるという欠点
がある。それに対し、ｉｎ−ｓｉｔｕ法は、一般的に目
的化合物の収率が低いという工業的に致命的な欠点があ
る。In the Bayer-Villiger reaction, since the yield of the target compound is generally higher in the Preformed method, this method is often used. However, this method has a drawback in that it is necessary to manufacture a peracetic acid solution in advance, and a manufacturing facility for it, a reaction process, and the like are required separately from a δ-lactone manufacturing facility, a reaction process, and the like. On the other hand, the in-situ method has an industrially fatal defect that the yield of the target compound is generally low.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、ｉｎ−ｓｉ
ｔｕ法によるバイヤービリガー反応によって環状ラクト
ン化合物から、δ−ラクトン化合物を収率良く製造する
方法を提供しようとするものである。SUMMARY OF THE INVENTION The present invention is an in-si system.
An object of the present invention is to provide a method for producing a δ-lactone compound from a cyclic lactone compound with a high yield by a Bayer-Villiger reaction by the tu method.
【０００６】[0006]
【課題を解決するための手段】本発明に係るδ−ラクト
ン化合物の製造方法は、下記一般式（１）の五員環ケト
ン化合物：The method for producing a δ-lactone compound according to the present invention comprises a five-membered ring ketone compound represented by the following general formula (1):
【化３】 〔式（１）中Ｒ1 はＣ1 〜Ｃ15の飽和又は不飽和鎖式炭
化水素基を表し、Ｒ2 は水素原子を表し、Ｒ3 〜Ｒ6 は
それぞれ互いに独立して、水素原子又はＣ1 〜Ｃ 15の鎖
式飽和炭化水素基を表す。〕に対し、強酸触媒の存在下
に過酸化水素および酢酸を反応させて下記一般式（２）
のδ−ラクトン化合物：Embedded image[R in Formula (1)1Is C1~ CFifteenOf saturated or unsaturated chain charcoal
Represents a hydride group, RTwoRepresents a hydrogen atom, RThree~ R6Is
Independently of each other, hydrogen atom or C1~ C FifteenChain of
Represents a saturated hydrocarbon group. ] In the presence of a strong acid catalyst
By reacting hydrogen peroxide and acetic acid with the following general formula (2)
Δ-lactone compound:
【化４】 〔但し、式（２）中、Ｒ1 〜Ｒ6 は前記の通り〕を製造
するに際し、反応系中に、式（１）の五員環ケトン化合
物および過酸化水素を同時に、かつ徐々に添加すること
を特徴とするものである。Embedded image [Wherein, in the formula (2), R 1 to R 6 are as described above], the five-membered ketone compound of the formula (1) and hydrogen peroxide are simultaneously and gradually added to the reaction system. It is characterized by doing.
【０００７】本発明方法において、（１）の五員環ケト
ン化合物が、その添加時間の少なくとも５０％におい
て、過酸化水素と同時に、反応系中に添加されることが
好ましい。In the method of the present invention, the five-membered ring ketone compound (1) is preferably added to the reaction system at the same time as hydrogen peroxide for at least 50% of the addition time.
【０００８】本発明方法において、前記過酸化水素が、
その添加時間の少なくとも５０％において、（１）式の
五員環ケトン化合物と同時に反応系中に添加されること
が好ましい。In the method of the present invention, the hydrogen peroxide is
At least 50% of the addition time is preferably added to the reaction system simultaneously with the five-membered ring ketone compound of the formula (1).
【０００９】本発明方法において、前記強酸触媒は、下
記添加方法（ａ），（ｂ）および（ｃ）： （ａ）予じめその全量を反応系内に添加しておく、
（ｂ）その全量を、前記過酸化水素および（１）式の五
員環ケトン化合物と同時に反応系中に添加する、および
（ｃ）予じめその一部を反応系中に添加しておき、その
残部を、前記過酸化水素および（１）式の五員環ケトン
化合物と同時に添加する、のいずれかにより添加させて
もよい。In the method of the present invention, the above strong acid catalyst is added in the following addition methods (a), (b) and (c): (a) Preliminarily the whole amount is added to the reaction system.
(B) The total amount thereof is added to the reaction system at the same time as the hydrogen peroxide and the five-membered ring ketone compound of the formula (1), and (c) A portion of the amount is added to the reaction system beforehand. The rest may be added at the same time as the hydrogen peroxide and the five-membered ring ketone compound of the formula (1) are added.
【００１０】本発明方法において、前記酢酸は、反応系
中に、下記添加方法（ａ），（ｂ）および（ｃ）： （ａ）予じめその全量を反応系中に添加しておく、
（ｂ）その全量を、前記過酸化水素および（１）式の五
員環ケトン化合物と同時に反応系中に添加する、および
（ｃ）予じめその一部を反応系中に添加しておき、その
残部を、前記過酸化水素および（１）式の五員環ケトン
化合物と同時に添加する、のいずれかにより添加させて
もよい。In the method of the present invention, the acetic acid is added to the reaction system in the following addition methods (a), (b) and (c): (a) Preliminarily the total amount thereof is added to the reaction system,
(B) The total amount thereof is added to the reaction system at the same time as the hydrogen peroxide and the five-membered ring ketone compound of the formula (1), and (c) A portion of the amount is added to the reaction system beforehand. The rest may be added at the same time as the hydrogen peroxide and the five-membered ring ketone compound of the formula (1) are added.
【００１１】本発明方法において、前記酢酸の総モル量
が、（１）式の五員環ケトン化合物の総モル量の１．０
〜５．０倍であることが好ましい。In the method of the present invention, the total molar amount of acetic acid is 1.0 of the total molar amount of the five-membered ring ketone compound of the formula (1).
Preferably it is up to 5.0 times.
【００１２】本発明方法におて、前記過酸化水素の総モ
ル量が、（１）式の五員環ケトン化合物の総モル量の
１．０〜４．０倍であることが好ましい。In the method of the present invention, the total molar amount of the hydrogen peroxide is preferably 1.0 to 4.0 times the total molar amount of the five-membered ring ketone compound of the formula (1).
【００１３】本発明方法において、前記強酸触媒は、硫
酸およびメタンスルフォン酸から選ばれた少なくとも１
種からなるものであることが好ましい。In the method of the present invention, the strong acid catalyst is at least one selected from sulfuric acid and methanesulfonic acid.
It is preferably composed of seeds.
【００１４】[0014]
【発明の実施の形態】本発明者らは、ｉｎ−ｓｉｔｕ法
型バイヤービリガー反応において、出発原料である環状
ケトン化合物を予め反応系中に仕込んでおくことなく、
これを過酸化水素と同時に徐々に添加することにより、
δ−ラクトン化合物を高収率で製造できる事を見出し、
本発明を完成した。BEST MODE FOR CARRYING OUT THE INVENTION In the in-situ method-type Bayer-Villiger reaction, the inventors of the present invention have not previously charged a starting material cyclic ketone compound into a reaction system.
By gradually adding this together with hydrogen peroxide,
It was found that the δ-lactone compound can be produced in high yield,
The present invention has been completed.
【００１５】本発明方法における基本的手法は、先ず反
応器中に酢酸と強酸触媒を仕込んでおき、そこに（１）
式の五員環ケトン化合物（以下、ケトン化合物と呼ぶ）
と過酸化水素とを同時に添加することにあるが、添加手
法（連続的、間欠的等）、添加時間、速度等には種々の
バリエーションがある。The basic method in the method of the present invention is as follows. First, acetic acid and a strong acid catalyst are charged into a reactor, and then (1) is added thereto.
5-membered ring ketone compound of formula (hereinafter referred to as ketone compound)
And hydrogen peroxide are added at the same time, but there are various variations in addition method (continuous, intermittent, etc.), addition time, speed, and the like.
【００１６】過酸化水素とケトン化合物の同時添加にお
いて、これら両化合物のいずれか一方の添加時間帯は、
その少なくとも５０％以上において、より好ましくは、
少なくとも７０％以上において他方の添加時間帯と重な
り合っていることが好ましい。これらの添加時間の重複
が、いずれか一方の化合物添加時間の５０％未満である
と、目的化合物の収率が不十分になる。過酸化水素およ
びケトン化合物の添加時間帯を互にずらす場合には、過
酸化水素が先行して供給される方が望ましく、例えば、
先ず、過酸化水素の添加を開始し、その３０分後にケト
ン化合物の添加を開始し、両者の同時添加が行われ、や
がて過酸化水素の添加が先に終了する等の実施形態であ
ってもよい。In the simultaneous addition of hydrogen peroxide and a ketone compound, the addition time of either one of these compounds is
At least 50% or more, more preferably,
It is preferable that at least 70% or more overlaps with the other addition time zone. If the overlap of these addition times is less than 50% of the addition time of one of the compounds, the yield of the target compound becomes insufficient. When the addition time zones of hydrogen peroxide and the ketone compound are shifted from each other, it is desirable that hydrogen peroxide be supplied in advance, for example,
First, even in an embodiment in which the addition of hydrogen peroxide is started, the addition of the ketone compound is started 30 minutes after that, the both are simultaneously added, and the addition of hydrogen peroxide is finished first. Good.
【００１７】本発明は、五員環ケトン化合物類から六員
環ラクトン化合物類を製造する反応に広く応用する事が
できるが、好ましい（１）式の五員環ケトン化合物は、
２−アルキルシクロペンタノンであり、その２−アルキ
ル基としては、Ｃ1 〜Ｃ15のもの、特にはＣ3 〜Ｃ10の
ものが好ましい。The present invention can be widely applied to a reaction for producing a six-membered ring lactone compound from a five-membered ring ketone compound, but the preferable five-membered ring ketone compound of the formula (1) is
It is a 2-alkylcyclopentanone, and the 2-alkyl group thereof is preferably a C 1 -C 15 one, particularly a C 3 -C 10 one.
【００１８】本発明方法で用いられる過酸化水素は、一
般的な工業薬品で良く、その濃度は３０〜７０％の範囲
のものであることが好ましいが、濃度６０％のものを使
用するのが一般的である。過酸化水素の添加総量は、ケ
トン化合物の添加総量に対して、１．０〜４．０倍モル
の範囲にあることが好ましく、特には、１．１〜２．０
倍モルの範囲内にあることがより好ましい。The hydrogen peroxide used in the method of the present invention may be a general industrial chemical, and the concentration thereof is preferably in the range of 30 to 70%, but the concentration of 60% is preferably used. It is common. The total amount of hydrogen peroxide added is preferably in the range of 1.0 to 4.0 times the mole of the total amount of the ketone compound added, and particularly 1.1 to 2.0.
More preferably, it is within the range of double mole.
【００１９】本発明方法に用いられる酢酸としては、濃
度８０〜１００％の工業薬品を使用する事が可能である
が、一般には濃度９８〜１００％のものを使用すること
が好ましい。酢酸の添加総量は、ケトン化合物の添加総
量に対して、１．０〜５．０倍モルの範囲内にあること
が好ましく、特に、１．５〜２．５倍モルであることが
より好ましい。尚、酢酸を、下記（ａ）〜（ｃ）の何れ
かの方法によって添加することが好ましい。 （ａ）予めその全量を反応系内に添加しておく。 （ｂ）その全量を過酸化水素、或いはケトン化合物と同
時に反応系内に添加する。および （ｃ）予めその一部を反応系内に添加しておき、残部を
過酸化水素、およびケトン化合物と同時に反応系内に添
加する。As the acetic acid used in the method of the present invention, it is possible to use an industrial chemical having a concentration of 80 to 100%, but it is generally preferable to use an acetic acid having a concentration of 98 to 100%. The total amount of acetic acid added is preferably in the range of 1.0 to 5.0 times mol, and more preferably 1.5 to 2.5 times mol, with respect to the total amount of addition of the ketone compound. . In addition, acetic acid is preferably added by any of the following methods (a) to (c). (A) The whole amount is added to the reaction system in advance. (B) The entire amount thereof is added to the reaction system at the same time as hydrogen peroxide or a ketone compound. And (c) A part thereof is added to the reaction system in advance, and the rest is added to the reaction system simultaneously with hydrogen peroxide and the ketone compound.
【００２０】本発明方法で使用される強酸触媒として
は、硫酸、スルフォン酸、強酸性イオン交換樹脂等を用
いることができるが、特には、硫酸、メタンスルフォン
酸を使用するのが良い。強酸触媒の添加総量は、過酸化
水素と酢酸の添加総重量（使用される過酸化水素溶液重
量と酢酸溶液重量の和）に対して、０．２〜１０．０重
量％の範囲で使用されることが好ましく、特には１．０
〜２．０重量％の範囲で使用することがより好ましい。As the strong acid catalyst used in the method of the present invention, sulfuric acid, sulfonic acid, strongly acidic ion exchange resin and the like can be used, but sulfuric acid and methanesulfonic acid are particularly preferable. The total amount of the strong acid catalyst added is in the range of 0.2 to 10.0% by weight based on the total weight of hydrogen peroxide and acetic acid (the total weight of the hydrogen peroxide solution and the acetic acid solution used). Preferably 1.0
More preferably, it is used in the range of 2.0 wt%.
【００２１】尚、強酸触媒は、下記の何れかの方法によ
って添加することが好ましい。 （ａ）予めその全量を反応系内に添加しておく。 （ｂ）その全量を過酸化水素、および五員環ケトン化合
物と同時に反応系内に添加する。 （ｃ）予めその一部を反応系内に添加しておき、残部を
過酸化水素、および五員環ケトン化合物と同時に反応系
内に添加する。The strong acid catalyst is preferably added by any of the following methods. (A) The whole amount is added to the reaction system in advance. (B) The whole amount thereof is added to the reaction system at the same time as hydrogen peroxide and the five-membered ring ketone compound. (C) A part of it is added to the reaction system in advance, and the rest is added to the reaction system simultaneously with hydrogen peroxide and the five-membered ring ketone compound.
【００２２】本発明の方法における反応温度は、３０〜
８０℃の範囲が好ましいが、特に、４０〜６０℃の範囲
内にあることがより好ましい。The reaction temperature in the method of the present invention is 30 to
The range of 80 ° C. is preferable, but the range of 40 to 60 ° C. is particularly preferable.
【００２３】本発明の方法の効果のメカニズムは明らか
ではないが、次のような事が推定される。すなわち、強
酸および過酸化物の共存系において、環状ケトン化合物
類は不安定である。このため過酸化物によるバイヤービ
リガー反応によって目的とするδ−ラクトン化合物を生
成するが、しかし、それと同時に副反応（おそらく、環
の解裂を伴う反応）を起こす傾向がある。環状ケトン化
合物を高濃度状態で反応させると副反応が起こりやす
く、そのため目的化合物収率の低下が起こるものであ
る。Although the mechanism of the effect of the method of the present invention is not clear, the following is presumed. That is, the cyclic ketone compounds are unstable in the coexisting system of strong acid and peroxide. Therefore, the Bayer-Villiger reaction with a peroxide produces the desired δ-lactone compound, but at the same time, it tends to cause a side reaction (probably a reaction involving ring cleavage). When the cyclic ketone compound is reacted in a high-concentration state, a side reaction is likely to occur, resulting in a decrease in the yield of the target compound.
【００２４】[0024]
【実施例】本発明の方法を下記実施例により、さらに説
明する。The method of the present invention will be further described by the following examples.
【００２５】実施例１〜１２ 実施例１〜１２の各々において、一般式（１）で示され
る種々のシクロペンタノン類のうちから、表１に示され
る化合物を用い、その１モルに対して、表１に記載のモ
ル数の酢酸、６０％過酸化水素、および強酸触媒を用い
た。５００ml容量の反応フラスコに、撹拌羽根、温度
計、冷却器を配備した。[0025] In each of Examples 1 to 12 Examples 1 to 12, from among the various cyclopentanone represented by the general formula (1), with the compounds indicated in Table 1, for the 1 mole The molar numbers of acetic acid, 60% hydrogen peroxide, and strong acid catalyst listed in Table 1 were used. A reaction flask having a capacity of 500 ml was equipped with a stirring blade, a thermometer, and a condenser.
【００２６】前記反応薬剤を用い、下記反応方法（Ａ）
〜（Ｄ）のうち、表１に記載の方法により反応を行っ
た。 （方法Ａ）：先ず、酢酸、強酸触媒を反応フラスコ中に
仕込み、温度５０℃で撹拌する。それに、過酸化水素と
シクロペンタノン化合物とを、同時に、温度５０℃を保
ちながら、５時間かけて平行滴下する。滴下終了後も、
さらに１時間５０℃に保ち反応を続ける。 （方法Ｂ）：先ず、酢酸、強酸触媒を反応フラスコ中に
仕込み、温度５０℃で保ちながら撹拌する。それに、先
ず過酸化水素の添加を開始し、過酸化水素の添加開始か
らの３０分後に、シクロペンタノンの添加を開始する。
過酸化水素およびシクロペンタノンの添加を５時間かけ
て終了し、その間、温度を５０℃に保つ。シクロペンタ
ノンの添加終了後、さらに１時間５０℃に保つ。 （方法Ｃ）：先ず、反応フラスコ中に酢酸のみを仕込
み、温度を５０℃に保ちながら撹拌する。それに、過酸
化水素、シクロペンタノン、および強酸を、同時に、温
度を５０℃に保ちながら、５時間かけて、平行滴下す
る。滴下終了後、さらに１時間５０℃に保つ。 （方法Ｄ）：撹拌しながら、強酸、酢酸、シクロペンタ
ノン、過酸化水素のすべてを反応フラスコに平行滴下す
る。供給時間は５時間であり、反応温度を５０℃に保
つ。滴下終了後、さらに１時間５０℃に保つ。Using the above reaction agent, the following reaction method (A)
-(D), the reaction was performed by the method described in Table 1. (Method A): First, acetic acid and a strong acid catalyst are charged into a reaction flask and stirred at a temperature of 50 ° C. Then, hydrogen peroxide and a cyclopentanone compound are simultaneously dropped in parallel for 5 hours while maintaining the temperature at 50 ° C. Even after the end of dropping
The reaction is continued at 50 ° C. for 1 hour. (Method B): First, acetic acid and a strong acid catalyst are charged into a reaction flask and stirred while maintaining the temperature at 50 ° C. Then, the hydrogen peroxide addition is started first, and 30 minutes after the hydrogen peroxide addition is started, the cyclopentanone addition is started.
The addition of hydrogen peroxide and cyclopentanone is completed over 5 hours, during which the temperature is kept at 50 ° C. After the addition of cyclopentanone is completed, the temperature is kept at 50 ° C. for another hour. (Method C): First, only acetic acid is charged into a reaction flask and stirred while keeping the temperature at 50 ° C. Then, hydrogen peroxide, cyclopentanone, and a strong acid are simultaneously dropped in parallel for 5 hours while maintaining the temperature at 50 ° C. After the dropping is completed, the temperature is kept at 50 ° C. for another hour. (Method D): While stirring, all of strong acid, acetic acid, cyclopentanone, and hydrogen peroxide are dropped in parallel into the reaction flask. The feeding time is 5 hours and the reaction temperature is kept at 50 ° C. After the dropping is completed, the temperature is kept at 50 ° C. for another hour.
【００２７】反応終了後、ガスクロマトグラフィーによ
り反応液を分析し、目的とするδ−ラクトン化合物の収
率（シクロペンタノンベース）を測定した。分析結果を
表１に示す。After the reaction was completed, the reaction solution was analyzed by gas chromatography to measure the yield of the target δ-lactone compound (cyclopentanone base). Table 1 shows the analysis results.
【００２８】比較例１ 実施例１と同じ操作を行った。但し、反応を下記方法Ｅ
により行った。 （方法Ｅ）：先ず、ｎ−ヘプチルシクロペンタノン、酢
酸、および硫酸を反応フラスコ中に仕込み、温度５０℃
において、過酸化水素を５時間かけて添加した。添加終
了後は、実施例１と同様に処理した。得られた分析結果
を表１に示す。 Comparative Example 1 The same operation as in Example 1 was performed. However, the reaction is carried out by the following method E
Was performed. (Method E): First, n-heptylcyclopentanone, acetic acid, and sulfuric acid were charged into a reaction flask, and the temperature was 50 ° C.
At, hydrogen peroxide was added over 5 hours. After the addition was completed, the same treatment as in Example 1 was performed. Table 1 shows the obtained analysis results.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１に明らかに示されているように、本発
明方法に係る実施例１〜１２において、δ−ラクトン
が、従来のｉｎ−ｓｉｔｕ法（比較例１）に比して高収
率で製造することができた。As clearly shown in Table 1, in Examples 1 to 12 according to the method of the present invention, δ-lactone was produced in a high yield as compared with the conventional in-situ method (Comparative Example 1). Could be manufactured in.
【００３１】[0031]
【発明の効果】本発明の方法に従えば、過酢酸溶液の製
造工程を必要とせず、収率よくδ−ラクトン類を製造す
る事が可能となる。According to the method of the present invention, it becomes possible to produce δ-lactones in good yield without the need for the step of producing a peracetic acid solution.
Claims (8)
物： 【化１】 〔式（１）中Ｒ1 はＣ1 〜Ｃ15の飽和又は不飽和鎖式炭
化水素基を表し、Ｒ2 は水素原子を表し、Ｒ3 〜Ｒ6 は
それぞれ互いに独立して、水素原子又はＣ1 〜Ｃ 15の鎖
式飽和炭化水素基を表す。〕に対し、強酸触媒の存在下
に過酸化水素および酢酸を反応させて下記一般式（２）
のδ−ラクトン化合物： 【化２】 〔但し、式（２）中、Ｒ1 〜Ｒ6 は前記の通り〕を製造
するに際し、反応系中に、式（１）の五員環ケトン化合
物および過酸化水素を同時に、かつ徐々に添加すること
を特徴とするδ−ラクトン化合物の製造方法。1. A five-membered ring ketone compound of the following general formula (1):
Thing: [Chemical 1][R in Formula (1)1Is C1~ CFifteenOf saturated or unsaturated chain charcoal
Represents a hydride group, RTwoRepresents a hydrogen atom, RThree~ R6Is
Independently of each other, hydrogen atom or C1~ C FifteenChain of
Represents a saturated hydrocarbon group. ] In the presence of a strong acid catalyst
By reacting hydrogen peroxide and acetic acid with the following general formula (2)
Δ-lactone compound of:[However, in the formula (2), R1~ R6Is as described above]
In doing so, in the reaction system, the five-membered ring ketone compound of formula (1)
Substances and hydrogen peroxide at the same time and gradually
A method for producing a δ-lactone compound, comprising:
添加時間の少なくとも５０％において、過酸化水素と同
時に、反応系中に添加される、請求項１に記載の製造方
法。2. The production method according to claim 1, wherein the five-membered ring ketone compound of the formula (1) is added to the reaction system at the same time with hydrogen peroxide for at least 50% of the addition time.
くとも５０％において、（１）式の五員環ケトン化合物
と同時に反応系中に添加される、請求項１に記載の製造
方法。3. The production method according to claim 1, wherein the hydrogen peroxide is added to the reaction system simultaneously with the five-membered ring ketone compound of the formula (1) at least 50% of the addition time.
（ｂ）および（ｃ）： （ａ）予じめその全量を反応系内に添加しておく、 （ｂ）その全量を、前記過酸化水素および（１）式の五
員環ケトン化合物と同時に反応系中に添加する、および
（ｃ）予じめその一部を反応系中に添加しておき、その
残部を、前記過酸化水素および（１）式の五員環ケトン
化合物と同時に添加する、のいずれかにより添加され
る、請求項１に記載の製造方法。4. The strong acid catalyst is added by the following addition method (a),
(B) and (c): (a) Preliminarily the total amount thereof is added to the reaction system, (b) the total amount of the hydrogen peroxide and the five-membered ring ketone compound of the formula (1) are simultaneously added. To the reaction system, and (c) a part of it is added to the reaction system in advance, and the rest is added simultaneously with the hydrogen peroxide and the five-membered ring ketone compound of the formula (1). The manufacturing method according to claim 1, which is added by any one of 1.
（ａ），（ｂ）および（ｃ）： （ａ）予じめその全量を反応系中に添加しておく、 （ｂ）その全量を、前記過酸化水素および（１）式の五
員環ケトン化合物と同時に反応系中に添加する、および
（ｃ）予じめその一部を反応系中に添加しておき、その
残部を、前記過酸化水素および（１）式の五員環ケトン
化合物と同時に添加する、のいずれかにより添加され
る、請求項１に記載の製造方法。5. The following addition methods (a), (b) and (c) for the acetic acid are added to the reaction system: (a) Preliminarily the total amount thereof is added to the reaction system, (b) The whole amount thereof is added to the reaction system at the same time as the hydrogen peroxide and the five-membered ring ketone compound of the formula (1), and (c) a part of it is added to the reaction system in advance, and the rest is added. Is added at the same time as the hydrogen peroxide and the five-membered ring ketone compound represented by the formula (1).
環ケトン化合物の総モル量の１．０〜５．０倍である、
請求項１に記載の製造方法。6. The total molar amount of the acetic acid is 1.0 to 5.0 times the total molar amount of the five-membered ring ketone compound of the formula (1),
The method according to claim 1.
の五員環ケトン化合物の総モル量の１．０〜４．０倍で
ある、請求項１に記載の製造方法。7. The method according to claim 1, wherein the total molar amount of the hydrogen peroxide is 1.0 to 4.0 times the total molar amount of the five-membered ring ketone compound of the formula (1).
フォン酸から選ばれた少なくとも１種からなる、請求項
１に記載の製造方法。8. The production method according to claim 1, wherein the strong acid catalyst comprises at least one selected from sulfuric acid and methanesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7260187A JPH09104681A (en) | 1995-10-06 | 1995-10-06 | Production of delta-lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7260187A JPH09104681A (en) | 1995-10-06 | 1995-10-06 | Production of delta-lactone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09104681A true JPH09104681A (en) | 1997-04-22 |
Family
ID=17344545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7260187A Pending JPH09104681A (en) | 1995-10-06 | 1995-10-06 | Production of delta-lactone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09104681A (en) |
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| JP2004217619A (en) * | 2002-12-26 | 2004-08-05 | Kao Corp | Method for producing cycloalkanone derivative |
| WO2009084504A1 (en) | 2007-12-28 | 2009-07-09 | Kao Corporation | Process for producing 2-(1-hydroxyalkyl)cycloalkanone |
| WO2011043478A1 (en) | 2009-10-09 | 2011-04-14 | 花王株式会社 | Process for producing 2-alkylcycloalkanone |
| WO2012060185A1 (en) * | 2010-11-02 | 2012-05-10 | 国立大学法人名古屋大学 | Method for producing ester |
| EP1433773B1 (en) † | 2002-12-26 | 2014-03-05 | Kao Corporation | Process for producing cycloalkanone derivatives |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
| JP2019043922A (en) * | 2017-09-06 | 2019-03-22 | 宇部興産株式会社 | Method for producing composition derived from ester compound using acid |
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1995
- 1995-10-06 JP JP7260187A patent/JPH09104681A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1433773B2 (en) † | 2002-12-26 | 2017-07-19 | Kao Corporation | Process for producing cycloalkanone derivatives |
| JP2004217619A (en) * | 2002-12-26 | 2004-08-05 | Kao Corp | Method for producing cycloalkanone derivative |
| CN100364950C (en) * | 2002-12-26 | 2008-01-30 | 花王株式会社 | Process for preparing 2-(alkyl) cyclic ketone |
| JP4615206B2 (en) * | 2002-12-26 | 2011-01-19 | 花王株式会社 | Method for producing cycloalkanone derivative |
| EP1433772A1 (en) * | 2002-12-26 | 2004-06-30 | Kao Corporation | Method for producing 2-(alkyl)cycloalkenone |
| EP1433773B1 (en) † | 2002-12-26 | 2014-03-05 | Kao Corporation | Process for producing cycloalkanone derivatives |
| WO2009084504A1 (en) | 2007-12-28 | 2009-07-09 | Kao Corporation | Process for producing 2-(1-hydroxyalkyl)cycloalkanone |
| WO2011043478A1 (en) | 2009-10-09 | 2011-04-14 | 花王株式会社 | Process for producing 2-alkylcycloalkanone |
| WO2012060185A1 (en) * | 2010-11-02 | 2012-05-10 | 国立大学法人名古屋大学 | Method for producing ester |
| US8853426B2 (en) | 2010-11-02 | 2014-10-07 | National University Corporation Nagoya University | Method for manufacturing ester |
| JP5920889B2 (en) * | 2010-11-02 | 2016-05-18 | 国立大学法人名古屋大学 | Esters manufacturing method |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
| JP2019043922A (en) * | 2017-09-06 | 2019-03-22 | 宇部興産株式会社 | Method for producing composition derived from ester compound using acid |
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